WO2010122918A1 - プリント配線板用基板、プリント配線板、及びそれらの製造方法 - Google Patents

プリント配線板用基板、プリント配線板、及びそれらの製造方法 Download PDF

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Publication number
WO2010122918A1
WO2010122918A1 PCT/JP2010/056556 JP2010056556W WO2010122918A1 WO 2010122918 A1 WO2010122918 A1 WO 2010122918A1 JP 2010056556 W JP2010056556 W JP 2010056556W WO 2010122918 A1 WO2010122918 A1 WO 2010122918A1
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WO
WIPO (PCT)
Prior art keywords
printed wiring
wiring board
layer
conductive layer
conductive
Prior art date
Application number
PCT/JP2010/056556
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English (en)
French (fr)
Japanese (ja)
Inventor
岡　良雄
春日　隆
岡田　一誠
勝成 御影
直太 上西
奥田　泰弘
Original Assignee
住友電気工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009244273A external-priority patent/JP2010272837A/ja
Priority claimed from JP2010052570A external-priority patent/JP5267487B2/ja
Priority claimed from JP2010052569A external-priority patent/JP5327107B2/ja
Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to EP10766975.6A priority Critical patent/EP2424337A4/en
Priority to US13/265,108 priority patent/US20120031656A1/en
Priority to CN201080018270.5A priority patent/CN102415222B/zh
Publication of WO2010122918A1 publication Critical patent/WO2010122918A1/ja
Priority to US14/185,206 priority patent/US20140166495A1/en
Priority to US15/213,216 priority patent/US20160330847A1/en
Priority to US15/214,278 priority patent/US20160330850A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
    • H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
    • H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
    • H05K3/4069—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in organic insulating substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/426—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in substrates without metal

Definitions

  • the present invention relates to a printed wiring board substrate, a printed wiring board, and manufacturing methods thereof.
  • a printed wiring board substrate that is, a printed wiring board substrate
  • a printed wiring board substrate is generally a method of bonding a heat-resistant polymer film and a copper foil with an organic adhesive, or coating a resin solution on a copper foil surface, drying, etc.
  • the heat-resistant polymer film film is produced by a method of laminating.
  • higher density and higher performance of printed wiring boards have been demanded.
  • a printed wiring board substrate that does not have an organic adhesive layer and has a sufficiently thin conductive layer (copper foil layer) is required as a printed wiring board substrate that satisfies the demands for higher density and higher performance. It has been.
  • 9-136378 discloses a copper thin film substrate in which a copper thin layer is laminated on a heat-resistant polymer film without using an adhesive. .
  • a copper thin film layer is formed as a first layer on the surface of a heat-resistant insulating base material using a sputtering method, and a copper thick film layer is formed thereon as a second layer using an electroplating method.
  • electroless plating and electrolytic plating are performed, and resist formation and etching are performed.
  • a printed wiring board substrate that does not have an organic adhesive layer and has a sufficiently thin conductive layer (copper foil layer) as a printed wiring board substrate that meets the demand for higher density and higher performance of printed wiring boards. It has been demanded.
  • Japanese Patent Application Laid-Open No. 6-120640 discloses a method for manufacturing a flexible printed wiring board capable of mounting components at high density.
  • the copper thin film substrate described in Patent Document 1 is a substrate that meets the requirements for high-density, high-performance printed wiring, in that an organic adhesive is not used and the conductive layer (copper foil layer) can be thinned. I can say that.
  • the first layer is formed using the sputtering method, vacuum equipment is required, and equipment costs such as construction, maintenance, and operation of the equipment increase.
  • all of supply of the base material to be used, thin film formation, base material storage, etc. must be handled in a vacuum.
  • the manufacturing method of the flexible printed wiring board of the said patent document 2 is a printed wiring board which meets the request
  • the thickness of the wiring circuit is the sum of the thickness of the original copper-clad laminate and the plating layer, the wiring circuit becomes thick, making it difficult to produce high-density and high-performance wiring circuits. There is a problem that there is.
  • the present invention solves the above-described problems in the prior art, does not require vacuum equipment for production, and thus is not subject to size limitations, does not use organic adhesives, and is a conductive layer (copper foil layer). It is an object of the present invention to provide a printed wiring board substrate, a printed wiring board, and a method for manufacturing a printed wiring board substrate that can be made sufficiently thin.
  • a printed wiring board substrate without being limited by the properties of the base material, a printed wiring board substrate, a printed wiring board, and a printed wiring board manufacturing method that enable high density, high performance, and sufficient thinning
  • the issue is to provide
  • the growth of oxide at the interface between the insulating substrate and the conductive layer can be suppressed in an oxidizing atmosphere (especially a high-temperature oxidizing atmosphere), so that peeling between the insulating substrate and the plating layer can be prevented, and etching properties are further improved. It is an object of the present invention to provide a printed wiring board substrate having good quality and a method for producing the same.
  • the printed wiring board substrate of the present invention that solves the above-described problems is an insulating base material, a first conductive layer that is stacked on the insulating base material, and a stacked layer on the first conductive layer.
  • the first feature is that the first conductive layer is configured as a coating layer of conductive ink containing metal particles, and the second conductive layer is configured as a plating layer. Yes.
  • the printed wiring board substrate according to the present invention has a second feature that a void portion of the first conductive layer made of a conductive ink coating layer is filled with an electroless metal plating portion.
  • the first conductive layer is configured as a coating layer of conductive ink containing metal particles having a particle diameter of 1 to 500 nm.
  • the printed wiring board substrate of the present invention has a metal ion in an aqueous solution containing a complexing agent and a dispersing agent.
  • the fourth feature is that the particles are obtained by a liquid phase reduction method for reducing the amount of sucrose.
  • the printed wiring board substrate of the present invention has a fifth feature that, in addition to any one of the first to fourth features, the metal particles are particles obtained by a titanium redox method.
  • the printed wiring board substrate of the present invention includes Ni, Cr, Ti, Si between the insulating base material and the first conductive layer.
  • a sixth feature is that an intervening layer made of any one or more elements is present.
  • the seventh feature of the printed wiring board of the present invention that solves the above problems is that it is manufactured using the printed wiring board substrate according to any one of the first to sixth features.
  • the printed wiring board of the present invention is the printed wiring board according to the seventh feature, wherein the printed wiring board is a multilayer board having conductive layers facing each other with an insulating base material interposed therebetween.
  • the first conductive layer is configured as a conductive ink coating layer
  • the second conductive layer is configured as a plating layer on the first conductive layer. It has the characteristics of In the printed wiring board of the present invention, in addition to the seventh or eighth feature, the second conductive layer is patterned by a semi-additive method using a resist with the first conductive layer as a base. This is the ninth feature.
  • the method for producing a printed wiring board substrate of the present invention that solves the above-mentioned problems is a conductive material in which metal particles having a particle diameter of 1 to 500 nm are dispersed on an insulating base material made of a film or a sheet.
  • the method for manufacturing a printed wiring board substrate of the present invention also includes an electroless method for filling the voids of the first conductive layer before performing the step of forming the second conductive layer.
  • the eleventh feature is that a metal plating step is performed.
  • the method for producing a printed wiring board substrate of the present invention in an aqueous solution in which metal particles contain a complexing agent and a dispersing agent, causes metal ions to act by the action of the reducing agent.
  • the twelfth feature is that the particles are obtained by a liquid phase reduction method for reduction.
  • the method for producing a printed wiring board substrate of the present invention has as a thirteenth feature that the metal particles are particles obtained by a titanium redox method. Yes.
  • the method for manufacturing a printed wiring board substrate according to the present invention includes conducting a heat treatment of the conductive ink at a temperature of 150 to 500 ° C. or a non-oxidizing atmosphere or Performing in a reducing atmosphere is a fourteenth feature.
  • the printed wiring board substrate of the present invention is a printed wiring board substrate comprising an insulating base material and a conductive layer covering the surface of the base material, the base material penetrating the base material.
  • the conductive layer includes a conductive ink layer including metal particles covering the entire surface of the inner hole of the through hole and the front and back surfaces of the substrate.
  • the conductive layer includes conductive particles including metal particles covering the entire inner surface of the through hole and the front and back surfaces of the base material.
  • a sixteenth feature is that the first conductive layer is composed of an ink layer, and the second conductive layer is composed of a plating layer laminated on the first conductive layer.
  • the printed wiring board substrate of the present invention has a seventeenth feature that the plating layer is formed by electroless plating and / or electrolytic plating.
  • the conductive ink layer is made of a conductive ink containing metal particles having a particle diameter of 1 to 500 nm.
  • the printed wiring board substrate according to the present invention in addition to any one of the fifteenth to eighteenth features described above, can be obtained by the action of a reducing agent in an aqueous solution containing the complexing agent and a dispersing agent.
  • the nineteenth feature is that the particles are obtained by a liquid phase reduction method for reducing ions.
  • the printed wiring board substrate of the present invention has, in addition to any one of the fifteenth to nineteenth features, a twentieth feature that the metal particles are particles obtained by a titanium redox method. Further, the printed wiring board substrate of the present invention, in addition to any one of the fifteenth to twentieth features described above, includes Ni, Cr, Ti, between the insulating base material and the conductive ink layer.
  • the twenty-first feature is that an intervening layer composed of one or more elements of Si is present.
  • a printed wiring board according to the present invention is a printed wiring board manufactured using the printed wiring board substrate having any one of the fifteenth to twenty-first characteristics.
  • the second conductive layer is patterned by a semi-additive method using a resist with the first conductive layer as a base.
  • the printed wiring board manufacturing method of the present invention includes a through-hole forming step for forming a through hole in an insulating base material, and an insulating base material in which a through hole is formed after the through-hole forming step.
  • a twenty-fourth feature includes at least a conductive ink application step of applying a conductive ink containing metal particles dispersed in a solvent, and a heat treatment step of performing a heat treatment after the conductive ink application step.
  • the method for producing a printed wiring board according to the present invention includes an electrolytic plating process for performing electrolytic copper plating after the heat treatment process, and a resist for forming a resist pattern after the electrolytic plating process.
  • the twenty-fifth feature includes at least a pattern forming step and an etching step for performing etching after the resist pattern forming step.
  • the method for manufacturing a printed wiring board of the present invention has a twenty-sixth feature of including an electroless plating step of performing electroless plating before the electrolytic plating step.
  • the printed wiring board manufacturing method of the present invention includes a through-hole forming step for forming a through hole in an insulating base material, and an insulating base material in which a through hole is formed after the through-hole forming step.
  • Conductive ink application step for applying conductive ink containing metal particles dispersed in solvent, heat treatment step for performing heat treatment after the conductive ink application step, and resist pattern for forming a resist pattern after the heat treatment step A forming step, an electrolytic plating step of performing electrolytic copper plating after the resist pattern forming step, a resist pattern peeling step of peeling the resist pattern formed in the resist pattern forming step after the electrolytic plating step, Conductivity to remove conductive ink layer exposed by resist pattern peeling process after resist pattern peeling process In that it comprises at least a link layer removing step is characterized in 27th.
  • the method for manufacturing a printed wiring board according to the present invention has a twenty-eighth feature including an electroless plating step of performing electroless plating before the resist pattern forming step.
  • the printed wiring board substrate of the present invention is a printed wiring board substrate obtained by laminating copper on the surface of an insulating base material, and an oxidation of a copper layer at the interface between the insulating base material and copper.
  • the 29th feature is that the metal particles for suppressing the dispersion are dispersed and adhered.
  • the printed wiring board substrate of the present invention has a thirtieth feature in that the metal particles include at least Ni particles.
  • the printed wiring board substrate of the present invention has a thirty-first feature that the metal particles comprise Ni particles and Cu particles.
  • the printed wiring board substrate manufacturing method of the present invention includes a conductive ink application step of applying a conductive ink containing metal particles to the surface of an insulating base material, and a heat treatment after the conductive ink application step.
  • a thirty-second feature is that it includes at least a heat treatment step to be performed and an electrolytic plating step to perform electrolytic copper plating after the heat treatment step.
  • the conductive layer laminated on the insulating base material is a first conductive layer configured as a conductive ink coating layer containing metal particles; Since it is comprised in combination with the 2nd conductive layer which consists of a plating layer laminated
  • the conductive layer can be formed on the substrate without using an organic adhesive.
  • the 1st conductive layer combined as a base layer of a 2nd conductive layer is comprised as a coating layer containing a metal particle, for printed wiring boards using various base materials, without being restrict
  • a substrate can be provided.
  • a high-density, high-performance printed wiring having a sufficiently thin conductive layer comprising a conductive layer composed of a sufficiently thin first conductive layer by a coating layer and a second conductive layer adjusted to a required thickness by plating. It is possible to provide a substrate suitable for forming the substrate.
  • the void portion of the first conductive layer made of the conductive ink coating layer is formed by the electroless metal plating portion.
  • the first conductive layer formed of the conductive ink becomes dense. Since the first conductive layer becomes dense, the breakdown starting point inside the first conductive layer is reduced, and peeling of the first conductive layer can be more reliably prevented.
  • the electroless metal plating portion can reduce the non-conductive void portion, the subsequent formation of the second conductive layer can be favorably performed by the electroplating method without increasing the coating thickness of the first conductive layer. Can be done.
  • the first conductive layer need not be thickly coated, it is possible to reduce the number of breakdown starting points in the first conductive layer. Costs can also be reduced.
  • the first conductive layer includes a conductive material containing metal particles having a particle diameter of 1 to 500 nm. Therefore, a dense and uniform thin layer can be stably formed on the insulating substrate without unevenness. Thereby, the formation of the plating layer of the second conductive layer can also be made dense and uniform. Therefore, it is possible to provide a printed wiring board substrate having a thin layer suitable for obtaining fine printed wiring and a conductive layer having no defect.
  • the metal particles in an aqueous solution containing a complexing agent and a dispersing agent. Since the particles are obtained by a liquid phase reduction method in which metal ions are reduced by the action of a reducing agent, an apparatus for obtaining particles is relatively simple compared to the gas phase method, leading to cost reduction. Also, mass production is easy and easy to get. Further, there is an advantage that the particle diameter can be made relatively uniform by stirring in an aqueous solution. Further, according to the printed wiring board substrate according to the fifth feature, in addition to the function and effect of any one of the first to fourth features, the metal particles are particles obtained by a titanium redox method.
  • Finishing the first conductive layer as a dense, uniform and sufficiently thin underlayer with few defects as the particle size can be easily and easily set to 1 to 500 nm, and the shape is round and the size is uniform. Can do. Therefore, it becomes easy to make the plating layer of the second conductive layer a dense and uniform layer, and a conductive layer suitable for forming a fine printed wiring that is sufficiently thin as a whole and has no defects can be obtained.
  • the printed wiring board substrate according to the sixth feature in addition to the function and effect of any one of the first to fifth features, between the insulating base material and the first conductive layer, the presence of an intervening layer composed of one or more elements of Ni, Cr, Ti, and Si provides a base for laminating the first conductive layer on the insulating base material, and adhesion Can be improved.
  • the printed wiring board according to the seventh feature is manufactured using the printed wiring board substrate according to any one of the first to sixth features, so that the conductive layer is made thin. It can meet the demand for high density and high performance printed wiring.
  • the printed wiring board is a multilayer board having conductive layers facing each other through an insulating base material, and the conductive layer is Since the first conductive layer has a first conductive layer and a second conductive layer, the first conductive layer is configured as a conductive ink coating layer, and the second conductive layer is configured as a plating layer on the first conductive layer.
  • the second conductive layer is a semi-additive method using a resist with the first conductive layer as a base. As a result of the pattern formation, a higher-density printed wiring board can be provided.
  • a printed wiring board substrate can be manufactured.
  • the step of forming the first conductive layer employs means for applying a conductive ink in which metal particles are dispersed, so that various base materials can be used without being limited by the material of the base material. There is. Further, by performing heat treatment, unnecessary organic substances in the ink can be removed and the metal particles can be securely fixed on the insulating substrate.
  • a sufficiently dense and uniform first conductive layer can be obtained, and a second conductive layer can be plated thereon, producing a dense and uniform substrate without defects. can do. Since the second conductive layer is laminated by plating, the thickness can be adjusted accurately and can be adjusted to a predetermined thickness in a relatively short time. Thus, a substrate suitable for forming a high-density, high-performance printed wiring having a sufficiently thin conductive layer can be manufactured.
  • the gap in the first conductive layer is performed.
  • the first conductive layer formed of the conductive ink can be made denser, thus reducing the breakdown starting point inside the first conductive layer, The peeling of one conductive layer can be prevented more reliably.
  • the voids can be reduced even if the coating thickness of the first conductive layer itself is reduced, and thus the second conductive layer to be performed thereafter can be satisfactorily used by electroplating. It can be carried out.
  • the first conductive layer need not be thickly coated, it is possible to reduce the number of breakage starting points in the first electric layer and to reduce the cost.
  • the printed wiring board substrate manufacturing method of the twelfth feature in addition to the effects of the tenth or eleventh feature, in an aqueous solution in which the metal particles include a complexing agent and a dispersing agent, Since the particles are obtained by a liquid phase reduction method in which metal ions are reduced by the action of a reducing agent, an apparatus for obtaining particles is relatively simple compared to the gas phase method, leading to a reduction in manufacturing costs. Also, mass production of particles is easy and easy to get. Furthermore, it is possible to provide a good printed wiring board substrate by using particles having a relatively uniform particle diameter by stirring in an aqueous solution.
  • the metal particles are particles obtained by a titanium redox method. Therefore, the particle size can be reliably and easily set to 1 to 500 nm, and the first conductive layer is formed as a particle having a round shape and a uniform size. Can be finished. Therefore, the plating layer of the second conductive layer can be easily made into a dense and uniform layer, and a printed wiring board substrate that is sufficiently thin as a whole and has no defects can be manufactured.
  • the heat treatment of the conductive ink is performed at a temperature of 150 to 500 ° C.
  • a printed wiring board substrate comprising an insulating base material and a conductive layer covering the surface of the base material, Has a through hole penetrating the base material, and the conductive layer is composed of a conductive ink layer containing metal particles covering the entire inner surface of the through hole and the front and back surfaces of the base material.
  • expensive vacuum equipment required for physical vapor deposition such as sputtering is not required. Therefore, the size of the printed wiring board substrate (mainly for the double-sided printed wiring board) is not limited by the vacuum equipment.
  • the conductive layer can be formed on the substrate without using an organic adhesive.
  • the conductive layer is configured as a layer containing metal particles
  • a printed wiring board substrate using various base materials can be provided without being limited by the material of the base material.
  • a printed wiring board substrate suitable for forming a high-density, high-performance printed wiring having a sufficiently thin conductive layer can be provided.
  • the conductive layer includes the entire surface of the inner hole of the through hole and the base.
  • a first conductive layer composed of a conductive ink layer containing metal particles covering the front and back surfaces of the material and a second conductive layer composed of a plating layer laminated on the first conductive layer,
  • a board substrate can be provided.
  • the plating layer is formed by electroless plating and / or electrolytic plating. Therefore, when only electroless plating is used for forming the plating layer, no energization is required, and a plating layer having a uniform thickness can be formed regardless of the shape and type of the material. Further, when only electrolytic plating is used for forming the plating layer, the plating layer can be quickly formed to a predetermined laminated thickness. Moreover, while being able to adjust thickness correctly and to laminate
  • the first conductive layer made of the conductive ink layer containing metal particles can be made thin. Therefore, the amount of ink can be saved, and the printed wiring board substrate can be reduced in cost.
  • the conductive ink layer has a thickness of 1 to 500 nm. Therefore, a dense and uniform thin layer can be stably formed on the insulating base material without unevenness. Therefore, it is possible to provide a printed wiring board substrate having a thin layer suitable for obtaining fine printed wiring and a conductive layer having no defect.
  • the metal particles are dispersed with a complexing agent. Since the particles are obtained by the liquid phase reduction method that reduces metal ions by the action of the reducing agent in the aqueous solution containing the agent, the device for obtaining the particles is relatively simple compared to the gas phase method, and the cost is reduced. Leads to. Also, mass production is easy and easy to get. Furthermore, there is an advantage that the particle diameter can be made relatively uniform by stirring in an aqueous solution.
  • the metal particles are obtained by a titanium redox method. Therefore, the particle size can be easily and easily adjusted to 1 nm to 500 nm, and the conductive ink layer can be formed into particles having a round shape and a uniform size. A sufficiently thin layer can be finished. Therefore, a conductive layer suitable for forming fine printed wiring can be obtained.
  • the insulating base material and the conductive material Since an intervening layer made of any one or more elements of Ni, Cr, Ti and Si is present between the ink layer and the ink layer, the intervening layer is a conductive ink layer on an insulating substrate. It becomes a base when laminating and adhesion can be improved.
  • the printed wiring board according to the twenty-second feature of the present invention since it is manufactured using the printed wiring board substrate according to any one of the fifteenth to twenty-first aspects of the present invention, an expensive vacuum facility is provided. Therefore, it is possible to satisfy the demand for high-density and high-performance printed wiring with a thin conductive layer.
  • the second conductive layer uses a resist with the first conductive layer as a base. Since the pattern is formed by the conventional semi-additive method, a higher-density printed wiring board can be provided.
  • the through hole is formed in the insulating base material, and the through hole is formed after the through hole forming step. Since there is provided at least a conductive ink application step for applying a conductive ink containing metal particles dispersed in a solvent to an insulating substrate, and a heat treatment step for performing a heat treatment after the conductive ink application step, the through Through holes can be formed in the insulating base material by the hole forming step. Also, the conductive ink application step can apply the conductive ink containing metal particles to the insulating base material in which the through holes are formed.
  • the heat treatment process can remove unnecessary organic substances in the conductive ink to securely fix the metal particles on the insulating substrate, and form a conductive ink layer on the surface of the insulating substrate. can do. Therefore, the thickness of the printed wiring board (mainly double-sided printed wiring board) can be reduced, and a high-density, high-performance printed wiring board can be obtained.
  • the printed wiring board mainly double-sided printed wiring board
  • an electrolytic plating step of performing electrolytic copper plating after the heat treatment step includes at least a resist pattern forming step for forming a resist pattern and an etching step for performing etching after the resist pattern forming step, a plating layer made of copper is formed by the electroplating step. can do.
  • a resist pattern can be formed by a resist pattern formation process. Further, an unnecessary conductive layer can be removed by an etching process.
  • the printed wiring board is manufactured by applying conductive ink, heat treatment and plating, an expensive vacuum facility is not required, and the printed wiring board can be manufactured without using an organic adhesive.
  • various base materials can be used without being limited by the material of the base material.
  • nano-order metal particles a sufficiently dense and uniform conductive ink can be applied, and a plating layer can be formed thereon, producing a dense and uniform printed wiring board without defects. be able to.
  • the electroless plating step of performing electroless plating before the electrolytic plating step in addition to the operational effects of the twenty-fifth feature of the present invention, the electroless plating step of performing electroless plating before the electrolytic plating step. Therefore, the conductive ink layer can be made thin. Therefore, the amount of ink can be saved and the cost can be reduced.
  • the through hole is formed in the insulating base material, and the through hole is formed after the through hole forming step.
  • a resist pattern forming step for forming a resist pattern, an electrolytic plating step for performing electrolytic copper plating after the resist pattern forming step, and a resist pattern formed in the resist pattern forming step after the electrolytic plating step are peeled off Resist pattern peeling step and conductivity exposed by the resist pattern peeling step after the resist pattern peeling step Since comprising at least a conductive ink layer removing step of removing the ink layer, the through hole forming step, it is possible to form the through holes in the insulating base material.
  • the conductive ink application step can apply the conductive ink containing metal particles to the insulating base material in which the through holes are formed.
  • the heat treatment process can remove unnecessary organic substances in the conductive ink to securely fix the metal particles on the insulating substrate, and form a conductive ink layer on the surface of the insulating substrate. can do.
  • a resist pattern can be formed by a resist pattern formation process.
  • the plating layer which consists of copper can be formed according to an electroplating process.
  • a resist pattern can be peeled by a resist pattern peeling process. Further, the conductive ink layer exposed in the resist pattern peeling step can be removed by the conductive ink layer removing step.
  • a printed wiring board can be manufactured by a so-called semi-additive method, and can be made a printed wiring board (mainly double-sided printed wiring board) with higher density and higher performance. Further, since the printed wiring board is manufactured by applying conductive ink, heat treatment, and plating, an expensive vacuum facility is unnecessary, and the printed wiring board can be manufactured without using an organic adhesive. Further, there is an advantage that various base materials can be used without being limited by the material of the base material. Of course, by using nano-order metal particles, a sufficiently dense and uniform conductive ink can be applied, and a plating layer can be formed thereon, producing a dense and uniform printed wiring board without defects. be able to.
  • electroless plating is performed before the resist pattern forming step. Since the plating step is provided, the conductive ink layer can be made thin. Therefore, the amount of ink can be saved and the cost can be reduced.
  • the printed wiring board substrate of the 29th feature of the present invention is a printed wiring board substrate formed by laminating copper on the surface of an insulating base material, the insulating base material and copper Since metal particles that suppress the oxidation of the copper layer are dispersed and adhered to the interface of the copper, the oxidation of the copper layer at the interface between the insulating base material and copper is suppressed in an oxidizing atmosphere (especially a high temperature oxidizing atmosphere). Can do. Therefore, peeling between the insulating base material and the copper layer accompanying the oxidation of the copper layer can be prevented. Therefore, a highly reliable printed wiring board substrate can be obtained.
  • the metal particles include at least Ni particles.
  • Ni particles that do not generate as metal particles By using Ni particles that do not generate as metal particles, a printed wiring board substrate with good etching properties can be obtained.
  • the metal particles comprise Ni particles and Cu particles.
  • Ni particles can be uniformly dispersed and adhered to the interface between the insulating base and copper.
  • a conductive ink application step of applying a conductive ink containing metal particles to the surface of an insulating base material, and the conductive ink Since at least a heat treatment step for performing heat treatment after the coating step and an electrolytic plating step for performing electrolytic copper plating after the heat treatment step are provided, the metal particles are formed on the surface of the insulating substrate by the conductive ink coating step. A conductive ink containing can be applied. Further, by the heat treatment step, unnecessary organic substances in the conductive ink can be removed and the metal particles can be securely fixed on the insulating base material.
  • the thickness can be adjusted accurately by the electrolytic plating process, and a plating layer having a predetermined thickness can be formed in a relatively short time.
  • the printed wiring board substrate is manufactured by applying conductive ink, heat treatment and plating, an expensive vacuum facility is not required, and the printed wiring board substrate can be manufactured without using an organic adhesive. it can.
  • various base materials can be used without being limited by the material of the base material.
  • nano-order metal particles a sufficiently dense and uniform conductive ink can be applied, a plating layer can be formed thereon, and a dense and uniform printed wiring board substrate without defects can be obtained. Can be manufactured.
  • a conductive ink containing metal particles between the insulating base and the plating layer, oxidation of the plating layer can be suppressed in an oxidizing atmosphere (particularly a high-temperature oxidizing atmosphere). Accordingly, it is possible to prevent the insulating substrate and the plating layer from being peeled off due to the oxidation of the plating layer. Therefore, a highly reliable printed wiring board substrate can be obtained. Therefore, a printed wiring board substrate suitable for forming a high-density, high-performance, high-reliability printed wiring having a sufficiently thin conductive layer can be manufactured as described above.
  • the printed wiring board substrate of the present invention no expensive vacuum equipment is required for manufacturing, and therefore, there is no size limitation, no organic adhesive is used, and the base material is limited. Accordingly, it is possible to enable printed wiring with high density, high performance, and sufficiently thin thickness using various base materials. Further, according to the printed wiring board of the present invention, as in the case of the printed wiring board substrate described above, no vacuum equipment is required for production, and thus there is no size limitation, and no organic adhesive is used. In addition, high-density and high-performance printed wiring can be made possible without being limited by the material of the base material or the lower layer.
  • the printed wiring board substrate and the printed wiring board manufacturing method using the same according to the present invention, an expensive vacuum facility is not required, and thus there is no size limitation, and no organic adhesive is used.
  • Manufacturing substrates for printed wiring boards with thin, dense and homogeneous conductive layers suitable for forming high-density, high-performance printed wiring, and printed wiring boards using the same, without being limited by the material of the base material can do.
  • the growth of oxide at the interface between the insulating substrate and the conductive layer can be suppressed in an oxidizing atmosphere (especially a high-temperature oxidizing atmosphere), so that peeling between the insulating substrate and the plating layer can be prevented, and etching properties are further improved. Can be produced, and a printed wiring board using the same.
  • substrate for printed wiring boards which concerns on 1st Embodiment of this invention, and its manufacturing method It is a figure explaining the manufacturing method of the printed wiring board which concerns on 1st Embodiment of this invention. It is a figure explaining the 1st example of the other manufacturing method of the printed wiring board concerning a 1st embodiment of the present invention. It is a figure explaining the 2nd example of the other manufacturing method of the printed wiring board concerning a 1st embodiment of the present invention.
  • the first conductive layer is subjected to an electroless metal plating portion or an electroless metal plating process. It is a figure explaining an example.
  • FIG. It is sectional drawing explaining the structure of the conventional printed wiring board board
  • FIG. It is sectional drawing explaining the manufacturing method of the printed wiring board using the board
  • the printed wiring board substrate 1 according to the first embodiment includes an insulating base material 11 made of a film or a sheet, a first conductive layer 12 laminated on the insulating base material 11, and the first A second conductive layer 13 laminated on the conductive layer 12, the first conductive layer 12 being configured as a conductive ink coating layer, and the second conductive layer 13 being configured as a plating layer. is there.
  • the insulating base 11 is a base for laminating the first conductive layer 12 and the second conductive layer 13, and a thin one is used as a film and a thick one is used as a sheet.
  • the material for the insulating base material 11 include flexible materials such as polyimide and polyester, paper phenol, paper epoxy, glass composite, glass epoxy, Teflon (registered trademark), rigid materials such as glass base materials, and hard materials. It is possible to use a rigid flexible material combined with a soft material. In the present embodiment, a polyimide film is used as the insulating base material 11.
  • the first conductive layer 12 plays a role as a pretreatment for forming a conductive layer on the surface of the insulating substrate 11, and is configured as a conductive ink coating layer.
  • a conductive ink coating layer By using a conductive ink coating layer, the surface of the insulating substrate 11 can be easily covered with a conductive film without the need for vacuum equipment. Further, using the obtained conductive film as a base, the second conductive layer 13 can be easily adjusted to a predetermined thickness by the plating layer.
  • the coating layer of the conductive ink constituting the first conductive layer 12 includes a layer subjected to a heat treatment such as drying or baking after the coating of the conductive ink.
  • the conductive ink is not particularly limited as long as the conductive ink can be laminated on the surface of the insulating substrate 11 by applying it.
  • a conductive ink that includes metal particles as a conductive substance that provides conductivity, a dispersant that disperses the metal particles, and a dispersion medium is used.
  • a coating layer made of fine metal particles is laminated on the insulating substrate 11.
  • the metal particles constituting the conductive ink one or more elements of Cu, Ag, Au, Pt, Pd, Ru, Sn, Ni, Fe, Co, Ti, and In can be used.
  • Cu is preferably used because of its good conductivity, easy printed wiring processing, and economical cost.
  • Cu is used as the coating layer of the first conductive layer 12.
  • the size of the metal particles contained in the conductive ink is 1 to 500 nm. This particle size is significantly smaller than that for normal coating, and is suitable for obtaining a dense conductive thin film.
  • the particle diameter is less than 1 nm, the dispersibility and stability in the ink are not necessarily good, and the particles are too small, and it takes time and effort to coat the layers.
  • it exceeds 500 nm it is easy to precipitate and it will become easy to produce a nonuniformity when apply
  • 30 to 100 nm is preferable.
  • the metal particles contained in the conductive ink can be obtained by a titanium redox method.
  • the titanium redox method is defined as a method in which metal element ions are reduced by an oxidation-reduction action when trivalent Ti ions are oxidized to tetravalent, thereby depositing metal particles.
  • the metal particles obtained by the titanium redox method have a small particle size, are uniform, and can be spherical or granular in shape. Therefore, the first conductive layer 12 as the base of the second conductive layer 13 is made thin. It can be formed in a dense layer.
  • the second conductive layer 13 is a substantially laminated conductive layer and is a plating layer by electroplating.
  • a plating method other than electroplating for example, a plating layer by an electroless plating method is also possible.
  • the thickness can be adjusted easily and accurately, and there is an advantage that a desired thickness can be obtained in a relatively short time.
  • a plating layer it is easy to obtain a dense layer with few defects.
  • the second layer can be easily formed by electroplating.
  • the plating layer by the second conductive layer 13 can be made of a metal having good conductivity such as Cu, Ag, or Au.
  • the second conductive layer 13 is sufficiently thicker than the first conductive layer 12.
  • the first conductive layer 12 makes the surface of the insulative base material 11 conductive so that it forms a base necessary for forming the second conductive layer 13. It is sufficient that the thickness is thin as long as it is coated.
  • the second conductive layer 13 requires a thickness necessary for forming a printed wiring.
  • the second layer is made of Cu as the conductive layer of the printed wiring board substrate.
  • the first conductive layer 12 is preferably made of Cu, but other metals having good adhesion to Cu can also be adopted.
  • the first conductive layer 12 and the second conductive layer 13 are not necessarily made of Cu, and the first conductive layer 12 is formed on the insulating base material 11 and the second conductive layer 13.
  • a metal having good adhesion can be used, and the second conductive layer 13 can be made of a metal having excellent conductivity.
  • intervening layer made of one or more elements of Ni, Cr, Ti, and Si in order to increase the adhesion between the two.
  • intervening layers can be obtained by, for example, subjecting a resinous insulating base material 11 such as polyimide to an alkali treatment to expose a functional group on the resin surface and allowing a metal acid to act on the functional group.
  • Si can be obtained by subjecting the resinous insulating base material 11 to silane coupling treatment.
  • a method for manufacturing a printed wiring board substrate according to the first embodiment of the present invention will be described.
  • a conductive ink in which metal particles having a particle diameter of 1 to 500 nm are dispersed is applied on an insulating base material 11, and heat treatment is performed.
  • a step of forming the first conductive layer 12 by fixing the metal particles in the applied conductive ink on the insulating substrate 11 as a metal layer, and performing the first conductive layer by plating. 12 includes a step of forming a second conductive layer 13 by laminating a metal layer on 12.
  • insulating base material 11 a continuous material continuous in one direction can be used.
  • a printed wiring board substrate can be manufactured in a continuous process using a continuous material.
  • the insulating base material 11 an independent piece having a predetermined size can be used.
  • the materials used as the insulating base material 11 are as described above, such as an insulating rigid material and a flexible material, in addition to polyimide.
  • the conductive ink an ink containing fine metal particles as a conductive substance, a dispersant for dispersing the metal particles, and a dispersion medium is used.
  • the types and sizes of the metal particles dispersed in the conductive ink are as described above in addition to using Cu particles of 1 to 500 nm.
  • the manufacturing method of a metal particle includes the titanium redox method mentioned above, and the following manufacturing methods are possible.
  • the metal particles can be produced by a conventionally known method such as a high temperature treatment method called an impregnation method, a liquid phase reduction method, or a gas phase method.
  • a high temperature treatment method called an impregnation method
  • a liquid phase reduction method for example, in water, a water-soluble metal compound that is a source of metal ions forming the metal particles and a dispersant are dissolved, and a reducing agent is added.
  • the metal ion may be subjected to a reduction reaction for a certain time under stirring.
  • two or more water-soluble metal compounds are used.
  • the manufactured metal particles are spherical or granular in shape, have a sharp particle size distribution, and can be made into fine particles.
  • the water-soluble metal compound that is the source of the metal ion is copper (II) nitrate [Cu (NO 3 ) 2 ], copper (II) sulfate pentahydrate [CuSO 4 .5H 2. O].
  • nickel chloride (II) hexahydrate [NiCl 2 ⁇ 6H 2 O] and nickel nitrate (II) hexahydrate [Ni (NO 3 ) 2 ⁇ 6H 2 O] can be exemplified.
  • water-soluble compounds such as chlorides, nitric acid compounds and sulfuric acid compounds can be used.
  • Reducing agent As a reducing agent in the case of producing metal particles by an oxidation-reduction method, various reducing agents capable of reducing and precipitating metal ions in a liquid phase (aqueous solution) reaction system can be used.
  • a liquid phase (aqueous solution) reaction system For example, sodium borohydride, sodium hypophosphite, hydrazine, transition metal ions such as trivalent titanium ions and divalent cobalt ions, reducing sugars such as ascorbic acid, glucose and fructose, ethylene glycol, glycerin, etc.
  • a polyhydric alcohol can be mentioned.
  • the titanium redox method described above is a method of reducing and precipitating metal ions by redox action when trivalent titanium ions are oxidized to tetravalent.
  • Dispersant for conductive ink As the dispersant contained in the conductive ink, various dispersants having a molecular weight of 2000 to 30000 and capable of satisfactorily dispersing the metal particles precipitated in the dispersion medium can be used. By using a dispersant having a molecular weight of 2000 to 30000, the metal particles can be favorably dispersed in the dispersion medium, and the film quality of the obtained first conductive layer 12 can be made dense and defect-free. . If the molecular weight of the dispersant is less than 2000, the effect of preventing the aggregation of the metal particles and maintaining the dispersion may not be obtained sufficiently. As a result, the conductive layer laminated on the insulating base material 11 may be dense.
  • the dispersant does not contain sulfur, phosphorus, boron, halogen and alkali from the viewpoint of preventing the deterioration of parts.
  • Preferred dispersants are those having a molecular weight in the range of 2000 to 30,000, amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, and also having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose.
  • a polymeric dispersant having a polar group is particularly those having a molecular weight in the range of 2000 to 30,000, amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, and also having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose.
  • the dispersant can be added to the reaction system in the form of a solution dissolved in water or a water-soluble organic solvent.
  • the content of the dispersant is preferably 1 to 60 parts by weight per 100 parts by weight of the metal particles.
  • the content ratio of the dispersant is less than the above range, there is a possibility that the effect of preventing the aggregation by dispersing the metal particles around the metal particles in the conductive ink containing water is insufficient.
  • the excessive dispersant inhibits the baking including the sintering of the metal particles to cause voids or reduce the denseness of the film quality.
  • the decomposition residue of the polymer dispersant may remain as an impurity in the conductive layer, and the conductivity of the printed wiring may be reduced.
  • the pH of the reaction system is preferably 7 to 13 in order to obtain particles having a fine particle size as in the present invention.
  • a pH adjusting agent can be used.
  • this pH adjuster common acids and alkalis such as hydrochloric acid, sulfuric acid, sodium hydroxide and sodium carbonate are used.
  • alkali metals and alkaline earth metals, Nitric acid and ammonia which do not contain a halogen element such as chlorine and impurity elements such as sulfur, phosphorus and boron are preferable.
  • metal particles having a particle diameter in the range of 30 to 100 nm are used, but it is possible to use those having a particle diameter in the range of 1 to 500 nm as an allowable range.
  • the particle diameter is represented by the center diameter D50 of the particle size distribution in the dispersion, and was measured using a Microtrac particle size distribution meter (UPA-150EX) manufactured by Nikkiso Co., Ltd.
  • the metal particles deposited in the liquid phase reaction system can be adjusted to a conductive ink using a powder once passed through processes such as separation, washing, drying, and crushing.
  • powdered metal particles, water as a dispersion medium, a dispersant, and if necessary, a water-soluble organic solvent are blended at a predetermined ratio, and a conductive ink containing metal particles can do.
  • the conductive ink is prepared using a liquid phase (aqueous solution) reaction system in which metal particles are deposited as a starting material.
  • the liquid phase (aqueous solution) of the reaction system containing the precipitated metal particles is subjected to treatments such as ultrafiltration, centrifugation, washing with water, and electrodialysis to remove impurities, and if necessary, concentrated to remove water.
  • treatments such as ultrafiltration, centrifugation, washing with water, and electrodialysis to remove impurities, and if necessary, concentrated to remove water.
  • a conductive ink containing the metal particles is prepared by blending a water-soluble organic solvent in a predetermined ratio. In this method, generation of coarse and irregular particles due to aggregation of metal particles during drying can be prevented, and a dense and uniform first conductive layer 12 can be obtained.
  • the ratio of water as a dispersion medium in the conductive ink is preferably 20 to 1900 parts by weight per 100 parts by weight of the metal particles. If the water content is less than the above range, the effect of sufficiently dispersing the water-based dispersant and satisfactorily dispersing the metal particles surrounded by the dispersant may be insufficient. Further, when the content ratio of water exceeds the above range, the ratio of metal particles in the conductive ink is decreased, and a good coating layer having the necessary thickness and density cannot be formed on the surface of the insulating substrate 11. There is.
  • the organic solvent blended into the conductive ink as necessary can be various water-soluble organic solvents.
  • specific examples thereof include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and tert-butyl alcohol, ketones such as acetone and methyl ethyl ketone,
  • examples thereof include polyhydric alcohols such as ethylene glycol and glycerin and other esters, and glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
  • the content of the water-soluble organic solvent is preferably 30 to 900 parts by weight per 100 parts by weight of the metal particles.
  • the content ratio of the water-soluble organic solvent is less than the above range, the effect of adjusting the viscosity and vapor pressure of the dispersion liquid due to the inclusion of the organic solvent may not be sufficiently obtained.
  • the above range is exceeded, there is a possibility that the effect of dispersing the metal particles in the conductive ink satisfactorily without causing aggregation by causing the dispersant to swell sufficiently with water.
  • the first conductive layer 12 fixed on the substrate is obtained as a baked coating layer.
  • the thickness of the conductive layer is preferably 0.05 to 2 ⁇ m.
  • the dispersant and other organic substances contained in the applied conductive ink are volatilized and decomposed by heat to remove them from the coating layer, and the remaining metal particles are in a sintered state or in a stage before sintering. Then, they are firmly fixed on the insulating substrate 11 as if they were in close contact with each other and solid-bonded.
  • the heat treatment may be performed in the air.
  • the firing temperature can be set to 700 ° C. or less from the viewpoint of suppressing the metal crystal grain size of the first conductive layer 12 formed by the firing from becoming excessively large or generating voids.
  • the heat treatment is performed at a temperature of 500 ° C. or lower in consideration of the heat resistance of the insulating base material 11 when the insulating base material 11 is an organic resin such as polyimide.
  • the lower limit of the heat treatment temperature is preferably 150 ° C. or higher in consideration of the purpose of removing organic substances other than metal particles contained in the conductive ink from the coating layer.
  • the process of forming the first conductive layer 12 is completed by applying the conductive ink onto the insulating base material 11 and heat-treating the coating layer.
  • the metal layer of the second conductive layer 13 stacked on the first conductive layer 12 is stacked by a plating method.
  • electroplating is used.
  • the first conductive layer 12 is formed on the insulating base material 11 in advance.
  • the electroplating method it is possible to quickly stack up to a predetermined stacking thickness.
  • the thickness can be adjusted accurately for stacking.
  • the obtained 2nd conductive layer 13 can be made into a homogeneous layer without a defect.
  • the thickness of the 2nd conductive layer 13 is set by what kind of printed circuit is produced, The thickness is not specifically limited.
  • a conductive layer having a thickness capable of forming such a high-density wiring for example, of 1 to several tens of microns can be used.
  • the relationship between the thicknesses of the first conductive layer 12 and the second conductive layer 13 is that the thickness of the first conductive layer 12 is usually thin, and the thickness of the second conductive layer 13 is sufficiently thick compared to that.
  • the thickness of the second conductive layer 13 can be considered as the thickness of the entire conductive layer.
  • the electroplating method uses, for example, a conventionally known electroplating bath according to the metal to be plated, such as Cu, Ag, Au, etc., and an appropriate condition is selected, so that an electroplating layer having a predetermined thickness is rapidly formed without defects. Can be done.
  • the second conductive layer 13 can be laminated by an electroless plating method.
  • the intervening layer is made of one or more elements of Ni, Cr, Ti, and Si in advance.
  • a layer may be present.
  • the step of forming the intervening layer is entered as a preliminary treatment.
  • a resinous insulating base material 11 such as polyimide is subjected to an alkali treatment so that a functional group is exposed on the resin surface, and a metal acid of the metal element described above is allowed to act on the functional group.
  • the Si intervening layer is obtained by subjecting the resinous insulating base material 11 to a silane coupling treatment.
  • FIG. 2 is a view for explaining the method of manufacturing the printed wiring board according to the first embodiment.
  • the printed wiring board 2 of the first embodiment described here is formed by a subtractive method using the printed wiring board substrate 1 of the present embodiment. That is, in FIG. 2, first, a printed wiring board substrate 1 adjusted to a predetermined size is prepared (A). Next, a photosensitive resist 2a is formed on the printed wiring board substrate 1 (B). Then, the wiring pattern 2b is patterned by exposure, development, etc. (C).
  • the printed wiring board 2 using the printed wiring board substrate 1 of the present invention can be obtained.
  • the printed wiring board 2 using the printed wiring board substrate 1 of the first embodiment is not limited to the subtractive method described above.
  • the printed wiring board 2 according to the present invention belongs to the printed wiring board 2 according to the present invention, in other words, including those by various other subtractive methods and other manufacturing methods.
  • a printed wiring board of a type different from the printed wiring board 2 formed using the printed wiring board substrate 1 of the first embodiment described above, that is, the printed wiring board substrate of the present invention is not necessarily required.
  • a printed wiring board having a pair of a first conductive layer as a conductive ink coating layer and a second conductive layer by a plating layer will be described. That is, another printed wiring board according to the present embodiment includes a first conductive layer configured as a conductive ink coating layer on a part of a plurality of layers constituting the printed wiring layer, and an upper surface of the first conductive layer. And a second conductive layer configured as a plating layer as a pair.
  • the printed wiring board is a multilayer board having conductive layers facing each other through an insulating base material, the conductive layer having a first conductive layer and a second conductive layer, One conductive layer is configured as a conductive ink coating layer, and the second conductive layer is configured as a plating layer on the first conductive layer.
  • the printed wiring board 3 is manufactured by the semi-additive method in the order of (A) to (F) in FIG. That is, first, an insulating base material 31 is prepared (A).
  • the insulating base material 31 can be made of the same material as the above-described insulating base material 11 such as polyimide.
  • a conductive ink in which metal particles having a particle diameter of 1 to 500 nm are dispersed is applied on the insulating base material 31 and subjected to heat treatment, and the first The conductive layer 32 is laminated as a coating layer (B).
  • the metal particles various metal particles described above can be used in addition to Cu particles typically obtained by a titanium redox method.
  • the conductive ink described above can be used.
  • the heat treatment conditions already described can be used for the heat treatment.
  • the resist 3a is coated on the first conductive layer 32 except for the portion to be the wiring pattern 3b (C).
  • the second conductive layer 33 is laminated on the portion to be the wiring pattern 3b other than the resist 3a by electroplating (D).
  • the resist 3a is removed (E).
  • etching is performed to remove the first conductive layer 32 where the resist 3a was present (F).
  • the printed wiring board 3 is obtained by the above.
  • the obtained printed wiring board 3 is composed of a plurality of layers, and a printed wiring layer is formed in a part thereof.
  • the first conductive layer 32 and the second conductive layer 33 are paired in part of the plurality of layers.
  • the printed wiring board 4 is manufactured by the semi-additive method in the order of (A) to (F) in FIG. 4 with the already formed printed wiring layer 41 as a lower layer. That is, first, a layer having the printed wiring layer 41 is prepared as a lower layer (A).
  • the printed wiring layer 41 is actually a printed wiring board having an insulating base material 41a and a conductive layer 41b.
  • the thing of the state before circuit formation can also be used.
  • the configuration and manufacturing method of the printed wiring layer 41 are not particularly limited, and conventionally known configurations and manufacturing methods can be employed.
  • a conductive ink in which metal particles having a particle diameter of 1 to 500 nm are dispersed is applied on the insulating base material 41a side of the lower printed wiring layer 41, and heat treatment is performed.
  • the first conductive layer 42 is laminated as a coating layer (B).
  • the metal particles Cu particles obtained by the titanium redox method described above and other metal particles can be used.
  • the conductive ink and heat treatment conditions described above can also be used for the conductive ink and heat treatment.
  • the resist 4a is coated on the first conductive layer 42 except for the portion to be the wiring pattern 4b (C).
  • the second conductive layer 43 is laminated on the portion to be the wiring pattern 4b other than the resist 4a by electroplating (D).
  • the printed wiring board 4 is obtained as described above.
  • the obtained printed wiring board 4 is composed of a plurality of layers, and a printed wiring layer 41 is formed in a part thereof.
  • the first conductive layer 42 and the second conductive layer 43 are paired in part of the plurality of layers.
  • at least a part of the second conductive layer 43 can be configured to be electrically connected to the conductive layer 41 b of the printed wiring layer 41 as a lower layer.
  • first conductive layer 42 and the second conductive layer 43 made of the coating layer in this way, it is easy to provide a high-density printed wiring board 4 that is multilayered in a state where the upper and lower printed wiring layers are electrically connected. It can be done.
  • the first conductive layer 12 (32, 42) is formed on the base material 11 (31, 41) with the conductive ink.
  • the second conductive layer 13 (33, 43) is then stacked by electroplating, and then the main structure or manufacturing method is used.
  • the first conductive layer 12 (32, 42) is conductive.
  • An electroless metal plating step may be performed on the first conductive layer 12 (32, 42) after the step of configuring with ink and before the step of laminating the second conductive layer 13 (33, 43). It is effective.
  • Cu, Ag, Ni, etc. can be considered, but when the first conductive layer 12 (32, 42) and the second conductive layer 13 (33, 43) are Cu, the adhesiveness and cost are considered. Thus, Cu and Ni are preferable.
  • the first conductive layer 12 (32, 42) shown in FIG. 5 (B) is applied to the substrate 11 (31, 41) shown in FIG. 5 (A)
  • the first conductive layer 12 (32, 42) is applied.
  • the electroless metal plating part 12a (32a, 42a) shown in FIG. 5 (B ') is formed, thereby forming the first conductive layer 12 (32, 42).
  • the existing void portion is filled with the electroless metal plating portion 12a (32a, 42a).
  • the electroless metal plating portion 12a (32a, 42a) is a void communicating with the void portion V, which will be described later, of the first conductive layer 12 (32, 42), more correctly, the surface of the first conductive layer 12 (32, 42). Part V is filled.
  • “filling” means that the base material 11 (31, 41) is not exposed at least at the bottom of the void portion V communicating with the surface, and the base material 11 (31, 41) is electroless metal plating portion 12a (32a). , 42a). Therefore, the electroless metal plating portion 12a (32a, 42a) fills the gap portion V of the first conductive layer 12 (32, 42) in a flush manner up to the surface of the first conductive layer 12 (32, 42).
  • FIG. 6A is a schematic diagram for explaining a state where electroless metal plating is not performed.
  • the void V remains as it is in the first conductive layer 12 (32, 42), which is a coating layer of the conductive ink, this becomes a starting point of destruction, and the first conductive layer 12 (32, 42). ).
  • M represents metal particles of the first conductive layer 12 (32, 42) by coating.
  • FIG. 6B is a schematic diagram for explaining the state when electroless metal plating is performed.
  • the space V communicating with the surface of the first conductive layer 12 (32, 42), which is a conductive ink coating layer, is filled by the electroless metal plating part 12a (32a, 42a). Therefore, the first conductive layer 12 (32, 42) becomes dense.
  • the fracture starting point (peeling start point) inside the first conductive layer 12 (32, 42) decreases, and the peeling in the subsequent manufacturing process or the like is reduced.
  • the peeling factor of the first conductive layer 12 (32, 42) penetrates the resist solvent in the step of FIG.
  • the first conductive layer 12 (32, 42) itself can be made thin without increasing its thickness.
  • the first conductive layer 12 (32, 42) is conductive between any two points.
  • first conductive layer 12 (32, 42) If a non-conductive portion occurs in the first conductive layer 12 (32, 42), plating cannot be formed at the non-conductive portion during electroplating, resulting in a circuit failure. If the first conductive layer 12 (32, 42) is thickly coated in order to ensure the conduction of the first conductive layer 12 (32, 42), the cost is increased and the starting point of destruction due to an increase in the gap V is increased. Although a method of forming the second conductive layer 13 (33, 43) by electroless plating is also conceivable, plating with a thickness of 1 to several tens of ⁇ m results in higher costs than electroplating.
  • electroless metal plating performs electroless Cu plating with treatments such as a cleaner process, a water washing process, an acid treatment process, a water washing process, a pre-dip process, an activator process, a water washing process, a reduction process, and a water washing process.
  • this electroless Cu plating for example, as a reagent, a trade name manufactured by Atotech Japan KK, Basic Print Gantt M1 (85 ml / l), Copper Print Gantt MSK (45 ml / l), Stabilizer Print Gantt M1 ( 1.5 ml / l), Starter Print Gantt M1 (8 ml / l), Reducer Cu (16 ml / l), and carried out at 35 ° C. for 10 minutes.
  • Basic Print Gantt M1 85 ml / l
  • Copper Print Gantt MSK 45 ml / l
  • Stabilizer Print Gantt M1 1.5 ml / l
  • Starter Print Gantt M1 8 ml / l
  • Reducer Cu (16 ml / l)
  • the heat treatment was performed in the same manner as in Example 1 except that 3% hydrogen and 97% nitrogen were used.
  • the resistance value of the first conductive layer obtained at this time was 10 ⁇ cm.
  • a printed wiring board substrate having a copper thickness of 12 ⁇ m was obtained by electroplating copper on the first conductive layer.
  • the printed wiring board substrate 101 is a printed wiring board substrate having a single conductive layer on both the front and back surfaces.
  • the conductive ink layer 120 is covered.
  • the printed wiring board substrate 101 is provided with a through hole 111 that penetrates the insulating base 110.
  • the number of through-holes 111, the formation positions, and the like are not limited to those in the present embodiment, and can be changed as appropriate.
  • the insulating base 110 is a base for laminating the conductive ink layer 120.
  • a thin one is used as a film and a thick one is used as a sheet.
  • the material of the insulating base 110 the same materials as those already described in the first embodiment can be used.
  • a polyimide film is used as the insulating substrate 110.
  • the conductive ink layer 120 is a conductive layer that covers the entire surface of the inner hole of the through hole 111 formed on the insulating base 110 and the front and back surfaces of the insulating base 110. It is formed by applying conductive ink containing metal particles to the surface of the substrate 110. By using a conductive ink coating layer, the front and back surfaces of the insulating base 110 can be easily covered with a conductive film without the need for vacuum equipment.
  • the conductive ink layer 120 includes a layer subjected to a heat treatment such as drying or baking after the application of the conductive ink.
  • the conductive ink can be laminated by applying it to the entire inner surface of the through hole 111 formed in the insulating base 110 and the front and back surfaces of the insulating base 110. Anything is acceptable.
  • the conductive ink includes metal particles as a conductive substance that provides conductivity, a dispersant that disperses the metal particles, and a dispersion medium. By applying using such a conductive ink, a coating layer made of fine metal particles is laminated on the front and back surfaces of the insulating substrate 110.
  • the metal particles constituting the conductive ink one or more of Cu, Ag, Au, Pt, Pd, Ru, Sn, Ni, Fe, Co, Ti, and In are used as in the first embodiment. These elements can be used. However, Cu is preferably used because of its good conductivity, easy printed wiring processing, and economical cost. Also in the second embodiment, Cu is used.
  • the size of the metal particles contained in the conductive ink is 1 to 500 nm. This particle size is significantly smaller than that for normal coating, and is suitable for obtaining a dense conductive thin film.
  • the particle diameter is less than 1 nm, the dispersibility and stability in the ink are not necessarily good, and the particles are too small, and it takes time and effort to coat the layers.
  • it exceeds 500 nm it is easy to precipitate and it will become easy to produce a nonuniformity when apply
  • 30 to 100 nm is preferable.
  • the metal particles contained in the conductive ink have a small particle size and are uniform, and can be obtained by a titanium redox method capable of making the shape spherical or granular.
  • the conductive ink layer 120 can be formed into a thin and dense layer.
  • the printed wiring board substrate 101 is configured to be a printed wiring board substrate having a single conductive layer on both the front and back surfaces, but is not necessarily limited to such a configuration.
  • the conductive ink layer 120 is a first conductive layer
  • a plating layer 130 as a second conductive layer is formed on the first conductive layer by an electrolytic plating process (so-called electroplating method). It is good also as a structure used as the board
  • an intervening layer made of one or more elements of Ni, Cr, Ti, and Si is provided. It may be configured to exist. These intervening layers can be obtained by, for example, subjecting a resinous insulating substrate 110 such as polyimide to an alkali treatment to expose a functional group on the resin surface and allowing a metal acid to act on the functional group. Si can be obtained by subjecting a resinous insulating base 110 to a silane coupling treatment.
  • the printed wiring board 103 according to the second embodiment forms a plating layer on the entire surface of the inner hole of the through hole 111 formed on the printed wiring board substrate 101 and the front and back surfaces of the printed wiring board substrate 101.
  • This is a double-sided printed wiring board in which the conductive ink layer 120 is a first conductive layer and the plating layer 130 is a second conductive layer.
  • the printed wiring board 103 is manufactured by a so-called subtractive method using the printed wiring board substrate 101 of the second embodiment.
  • through hole 111 is formed after through hole forming step A1 for forming through hole 111 in insulating base material 110 and through hole forming step A1.
  • a conductive ink application step A2 for applying a conductive ink containing metal particles dispersed in a solvent to the insulating base 110, and a heat treatment step (not shown) for performing a heat treatment after the conductive ink application step A2.
  • a plating process A3 for performing electrolytic copper plating after the heat treatment process
  • a resist pattern forming process A4 for forming a resist pattern after the plating process A3, and a wiring circuit for forming a wiring circuit after the resist pattern forming process A4. It is manufactured through the formation step A5.
  • through-hole 111 is formed in insulating base 110 by using drilling or laser processing in the through-hole forming step A1. Thereafter, a conductive ink containing metal particles is applied to the entire surface of the inner hole of the through hole 111 and the front and back surfaces of the insulating base 110 by the conductive ink application step A2. Next, in a heat treatment step (not shown), the metal particles in the applied conductive ink are fixed on the insulating substrate 110 as a metal layer. As a result, a conductive ink layer 120 containing metal particles to be a conductive layer is formed on the entire surface of the inner hole of the through hole 111 formed on the insulating base 110 and on the front and back surfaces of the insulating base 110. . As described above, the printed wiring board substrate 101 having the one conductive layer shown in FIG.
  • plating is performed on the entire surface of the inner hole of the through hole 111 and the front and back surfaces of the insulating base material 110 by an electrolytic plating process using copper (so-called electroplating method).
  • Layer 130 is formed.
  • a conductive layer is formed in which the conductive ink layer 120 is the first conductive layer and the plating layer 130 laminated on the first conductive layer is the second conductive layer. That is, the printed wiring board substrate 102 having the two conductive layers shown in FIG.
  • a resist pattern 142 is formed by performing exposure and development using a pattern mask 141 in a state where the resist 140 is laminated on the plating layer 130. Then, a portion to be a wiring pattern is covered. Next, as shown in FIG. 9, an unnecessary conductive layer other than a portion to be a wiring pattern is removed by an etching step A5-1 of the wiring circuit forming step A5. Thereafter, the resist pattern 142 is stripped by a resist pattern stripping step A5-2 of the wiring circuit forming step A5.
  • the printed wiring board 103 using the printed wiring board substrate 101 according to the second embodiment is manufactured.
  • the plating layer 130 is formed only by the electrolytic plating process (so-called electroplating method).
  • electroplating method the present invention is not necessarily limited to such a configuration.
  • the metal used in the electrolytic plating process is not limited to copper (Cu), and a metal having excellent conductivity such as silver (Ag) or gold (Au) may be used.
  • substrate 101 of 2nd Embodiment is not limited to an above described subtractive method.
  • those using the printed wiring board substrate 101 of the second embodiment belong to the printed wiring board 103 of this embodiment, including those by various other subtractive methods and other manufacturing methods.
  • the configuration and manufacturing method of the printed wiring board substrate 101 and the printed wiring board 103 will be described in more detail.
  • insulating base material 110 a continuous material continuous in one direction can be used. Using a continuous material, the printed wiring board substrate 101 can be manufactured in a continuous process.
  • the insulating base 110 an independent piece having a predetermined size can be used.
  • the materials used as the insulating base 110 are as described above, such as an insulating rigid material and a flexible material, in addition to polyimide.
  • the conductive ink an ink containing fine metal particles as a conductive substance, a dispersant for dispersing the metal particles, and a dispersion medium is used.
  • the types and sizes of the metal particles dispersed in the conductive ink are as described above in addition to using Cu particles of 1 to 500 nm.
  • the manufacturing method of a metal particle includes the titanium redox method mentioned above, and the following manufacturing methods are possible.
  • the method for producing metal particles, the reducing agent for producing metal particles by the oxidation-reduction method, the dispersant contained in the conductive ink, and the dispersion medium are as described above.
  • the adjustment of the particle size of the metal particles and the adjustment of the conductive ink are as described above.
  • the method for applying the conductive ink in which the metal particles are dispersed on the insulating substrate 10 is also as described above.
  • the conductive ink layer 120 fixed on the base is obtained as a baked coating layer.
  • the thickness of the conductive ink layer 120 is preferably 0.05 to 2 ⁇ m. The heat treatment of the coating layer has already been described.
  • the plating layer 130 to be laminated on the conductive ink layer 120 is laminated by the plating step A3. Actually, it is performed by an electrolytic plating process (so-called electroplating method) using copper (Cu).
  • electroplating method copper
  • the plating layer 130 as the second conductive layer can be easily formed by electroplating. By using the electrolytic plating process, it is possible to quickly stack up to a predetermined stacking thickness. In addition, there is an advantage that the thickness can be adjusted accurately for stacking.
  • the plated layer 130 obtained can be a homogeneous layer without defects.
  • the thickness of the plating layer 130 is set depending on what kind of printed circuit is produced, and the thickness is not particularly limited. However, as long as the purpose is to form a high-density and high-performance printed wiring, a conductive layer having a thickness capable of forming such a high-density wiring, for example, of 1 to several tens of microns can be used.
  • the relationship between the thickness of the conductive ink layer 120 that is the first conductive layer and the plating layer 130 that is the second conductive layer is that the conductive ink layer 120 that is the first conductive layer makes the surface of the insulating substrate 110 conductive.
  • the plating layer 130 serves as a base formation necessary for forming the plating layer 130 as the second conductive layer, and as long as the front and back surfaces of the insulating base 110 are reliably covered, it is sufficient that the thickness is thin. It is.
  • the plating layer 130 requires a thickness necessary for forming a printed wiring. Therefore, the thickness of the plating layer 130 can be considered as the thickness of the entire conductive layer.
  • the electroplating step (so-called electroplating method) can be performed using a conventionally known electroplating bath and selecting an appropriate condition so that an electroplated layer having a predetermined thickness can be formed quickly without defects.
  • the conductive ink layer 120 that is the first conductive layer is made of Cu as the conductive layer of the printed wiring board substrate 101.
  • the conductive ink layer 120 is preferably made of Cu, but any other metal having good adhesion to Cu can be used.
  • the conductive ink layer 120 and the plating layer 130 are not necessarily made of Cu, and the conductive ink layer 120 adheres to the insulating substrate 110 and the plating layer 130.
  • a good metal can be used, and the plating layer 130 can be a metal having excellent conductivity.
  • any one or more of Ni, Cr, Ti, and Si is used in advance.
  • An intervening layer made of these elements may be present.
  • the step of forming the intervening layer is entered as a preliminary treatment. This pretreatment is performed by, for example, subjecting a resinous insulating substrate 110 such as polyimide to an alkali treatment to expose a functional group on the resin surface and causing the metal acid of the above-described metal element to act thereon. Get.
  • the Si intervening layer is obtained by subjecting the resinous insulating base 110 to a silane coupling treatment.
  • the printed wiring board 103 using the printed wiring board substrate 101 according to the second embodiment and its manufacturing method it is more expensive to manufacture than the conventional double-sided printed wiring board and its manufacturing method.
  • Vacuum equipment is not required, equipment costs can be reduced, manufacturing efficiency is good, and size restrictions are not imposed.
  • desmear treatment is not required, and various substrates can be used without using organic adhesives and without being restricted by the material of the substrate, enabling high density, high performance, and sufficiently thin conductive layers. It can be.
  • etching can be performed with high accuracy during the etching process (so-called etching sagging can be prevented).
  • mass production of high-density, high-performance double-sided printed wiring boards can be realized.
  • the conventional double-sided printed wiring board 105 has a copper-clad structure in which a conductive layer 150 is formed by laminating copper thin films on the front and back surfaces of an insulating substrate 110 by sputtering.
  • the through hole 111 is formed by the through hole forming step A1, and then desmearing is performed, and the plating layer 130 is formed by performing the electroless plating step and the electrolytic plating step by the plating step A3.
  • These are generally manufactured through a resist pattern forming step A4 and a wiring circuit forming step A5. Therefore, vacuum equipment for performing the sputtering method is required, and equipment costs such as construction, maintenance and operation of equipment are high.
  • the printed wiring board 103 is manufactured by a semi-additive method using the printed wiring board substrate 101.
  • Other configurations are the same as those of the second embodiment of the present invention described above. The same member and the same function are given the same number, and the following description is omitted.
  • through-hole 111 is formed in insulating base 110 using drilling or laser processing in through-hole forming step A1.
  • a conductive ink containing metal particles is applied to the entire surface of the inner hole of the through hole 111 and the front and back surfaces of the insulating substrate 110 by the conductive ink application step A2.
  • the metal particles in the applied conductive ink are fixed on the insulating substrate 110 as a metal layer by a heat treatment step (not shown).
  • the conductive ink layer 120 containing metal particles to be a conductive layer is formed on the front and back surfaces of the insulating base 110.
  • the printed wiring board substrate 101 is manufactured as shown in FIG.
  • the resist 140 is laminated on the front and back surfaces of the printed wiring board substrate 101 and exposed using the pattern mask 141 and developed. As shown in FIG. A pattern 142 is formed to cover the portion other than the portion to be the wiring pattern.
  • the plating layer 130 is formed by an electroplating process (so-called electroplating method) using copper (Cu) in a portion to be a wiring pattern by the plating process A3.
  • a conductive layer is formed in which the conductive ink layer 120 is the first conductive layer, and the plating layer 130 laminated on the first conductive layer is the second conductive layer. That is, using the conductive ink layer 120 as the first conductive layer as a base, the plating layer 130 as the second conductive layer is patterned by the semi-additive method using the resist 140.
  • the resist pattern 142 is stripped by a resist pattern stripping step A5-2 of the wiring circuit forming step A5.
  • the conductive ink layer 120 exposed by the resist pattern peeling step A5-2 is removed by the etching step A5-1 of the wiring circuit forming step A5.
  • an electroless plating step for covering the entire inner surface of the through hole 111 and the front and back surfaces of the insulating base 110 with an electroless plating layer is provided before the resist pattern forming step A4. It is good. With such a configuration, the thickness of the conductive ink layer 120 as the first conductive layer can be reduced. Therefore, the printed wiring board substrate 101 and the printed wiring board 103 can save the ink amount and can reduce the cost.
  • the heat treatment was performed in the same manner as in Example 3 except that 3% hydrogen and 97% nitrogen were used.
  • the resistance value of the conductive ink layer obtained at this time was 10 ⁇ cm.
  • copper was electroplated on the conductive ink layer to obtain a printed wiring board substrate having a copper thickness of 12 ⁇ m.
  • the printed wiring board substrate 201 is a printed wiring board substrate formed by laminating copper on the surface of an insulating base material, and includes an insulating base material 210 made of a film or a sheet and a conductive material serving as a first conductive layer.
  • the conductive ink layer 220 made of conductive ink and the plating layer 230 made of copper, which is the second conductive layer.
  • the insulating base 210 is a base for laminating the conductive ink layer 220.
  • a thin one is used as a film and a thick one is used as a sheet.
  • the material of the insulating base 210 the same materials as those already described in the first embodiment and the second embodiment can be used.
  • a polyimide film is used as the insulating substrate 210.
  • the conductive ink layer 220 is a conductive layer having an effect of suppressing the growth of copper oxide while forming a base layer of the plating layer 230 made of copper, and includes metal particles on the surface of the insulating substrate 210. It is formed by applying conductive ink.
  • nickel (Ni) is used as the metal particles. Since nickel (Ni) does not generate a passive film by using nickel (Ni) as the metal particles in this way, as shown in the upper part of FIG. Metal particles M1 (nickel particles) can be dispersed and adhered to the interface K with the plating layer 230 to be formed.
  • oxidation of the plating layer 230 at the interface K between the insulating base 210 and the plating layer 230 can be suppressed in an oxidation atmosphere (particularly a high-temperature oxidation atmosphere).
  • a high-temperature oxidizing atmosphere refers to a manufacturing step of the printed wiring board substrate 201, for example, a heat treatment step such as drying or baking, or a use stage of the printed wiring board substrate 201, for example, the printed wiring board substrate 201. This indicates various situations in which the printed wiring board substrate 201 is placed in a high-temperature oxidizing atmosphere, such as the manufacturing stage of the used printed wiring board.
  • a printed wiring board substrate 201 in which metal particles M1 (nickel particles) are dispersed and adhered to the interface K between the insulating base 210 and the plating layer 230 is heated at a high temperature.
  • metal particles M1 nickel particles
  • FIG. 15 a printed wiring board substrate 201 in which metal particles M1 (nickel particles) are dispersed and adhered to the interface K between the insulating base 210 and the plating layer 230 is heated at a high temperature.
  • metal particles M1 nickel particles
  • Ni which is a metal particle
  • the interface K in the form of a particle, so that the surface area per unit volume can be increased and printed using the printed wiring board substrate 201.
  • Good etching properties can be realized when forming a wiring board.
  • a metal substance for example, chromium (Cr) having a high anti-oxidation effect is present at the interface K between the insulating base 210 and the plating layer 230 as the conductive layer.
  • Etc. by using a sputtering method to form a seed layer N (so-called barrier layer).
  • a metal material having a high barrier effect is formed on the insulating base 210. It was necessary to make it adhere uniformly.
  • a metal material having a high barrier effect forms a difficult-to-etch layer, and it takes time to remove the seed layer N in an etching process such as when a printed wiring board is formed using the printed wiring board substrate 202.
  • There were problems such as an increase in the manufacturing process.
  • the prevention of peeling of the plating layer 230 accompanying the growth of oxide in a high-temperature oxidizing atmosphere and the good etching property in the etching process are realized at the same time. be able to. Therefore, it is possible to obtain a printed wiring board substrate 201 having excellent reliability and high workability.
  • the conductive ink layer 220 can be easily formed on the surface of the insulating base 210 without the need for vacuum equipment. Therefore, the conductive ink layer 220 can be used as a base layer of the plating layer 230, and the formation of the plating layer 230 can be facilitated.
  • the conductive ink layer 220 includes a layer subjected to heat treatment such as drying or baking after application of the conductive ink.
  • the conductive ink is not particularly limited as long as the conductive ink can be laminated by applying it to the surface of the insulating base 210.
  • the conductive ink includes metal particles M1 as a conductive material that provides conductivity, a dispersant that disperses the metal particles M1, and a dispersion medium. By applying using such conductive ink, a film containing fine metal particles L is formed on the surface of the insulating base 210.
  • nickel (Ni) is used in the third embodiment.
  • the invention is not necessarily limited to such a configuration. Any one or more elements of (Cu), titanium (Ti), and vanadium (V) and oxides thereof may be used.
  • the size of the metal particles M1 contained in the conductive ink is 1 to 500 nm.
  • This particle size is significantly smaller than that for normal coating, and is suitable for obtaining a dense conductive thin film.
  • the particle diameter is less than 1 nm, the dispersibility and stability in the ink are not necessarily good, and the particles are too small, and it takes time and effort to coat the layers.
  • it exceeds 500 nm it is easy to precipitate and it will become easy to produce a nonuniformity when apply
  • 30 to 100 nm is preferable.
  • the number of particles per unit area (per 1 mm 2 ) of the metal particles M1 is preferably 1 ⁇ 10 9 to 1 ⁇ 10 11 when the particle diameter of the metal particles M1 is 10 nm. Further, when the particle diameter of the metal particles M1 is 50 nm, it is desirable that the particle diameter is 5 ⁇ 10 7 to 4.6 ⁇ 10 9 particles. Further, when the particle diameter of the metal particles M1 is 100 nm, it is desirable that the particle size is 1 ⁇ 10 8 to 1 ⁇ 10 10 particles. That is, when it is assumed that the metal particles M1 are spherical, the coverage is preferably 0.1 to 10. More preferably, the coverage is 0.2 to 3.
  • the metal particles M1 contained in the conductive ink have a small particle size, are uniform, and can be obtained by a titanium redox method capable of making the shape spherical or granular.
  • the conductive ink layer 220 can be formed in a thin and dense layer.
  • the plating layer 230 is a conductive layer that is laminated on the surface of the insulating substrate 210 via the conductive ink layer 220, and is formed by an electrolytic plating process using copper (so-called electroplating method).
  • electroplating method since the conductive ink layer 220 as the first conductive layer is formed in the lower layer in advance, the plating layer 230 as the second conductive layer can be easily formed by electroplating.
  • the electrolytic plating process it is possible to quickly stack up to a predetermined stacking thickness.
  • the thickness can be adjusted accurately for stacking.
  • the plating layer 230 obtained can be a homogeneous layer without defects.
  • the thickness of the plating layer 230 is set depending on what kind of printed wiring circuit is produced, and the thickness is not particularly limited. However, as long as the purpose is to form a high-density and high-performance printed wiring, a conductive layer having a thickness capable of forming such a high-density wiring, for example, of 1 to several tens of microns can be used.
  • the electrolytic plating process (so-called electroplating method) can be performed using a conventionally known electroplating bath and selecting appropriate conditions so that an electroplating layer having a predetermined thickness can be formed quickly without defects. .
  • a printed wiring board 203 using the printed wiring board substrate 201 according to the third embodiment is a printed wiring board in which the conductive ink layer 220 is a first conductive layer and the plating layer 230 is a second conductive layer.
  • the printed wiring board 203 is manufactured by a so-called subtractive method using the printed wiring board substrate 201 of the present embodiment.
  • the pretreatment step B1 the conductive ink application step B2 for applying the conductive ink dispersed in the solvent to the insulating base 210, and the heat treatment after the conductive ink application step B2 are illustrated.
  • Non-heat treatment step plating step B3 for performing electrolytic copper plating after the heat treatment step
  • resist pattern formation step B4 for forming a resist pattern after the plating step B3
  • wiring for forming a wiring circuit after the resist pattern formation step B4 It is manufactured through the circuit formation step B5.
  • an alkali treatment is performed on the surface of insulating base 210 in pretreatment step B1. More specifically, the insulating base 210 is immersed in an aqueous sodium hydroxide solution, then washed with water, pickled, washed with water, and dried. By this pretreatment process B1, the imide bond of the insulating base material 210 made of a polyimide film is decomposed to generate a carboxyl group and a carbonyl group.
  • a configuration using plasma treatment may be employed.
  • a conductive ink containing nickel (Ni) as the metal particles M1 is applied to the surface of the insulating base 210 by the conductive ink application step B2. Thereafter, the metal particles M1 in the applied conductive ink are fixed on the insulating substrate 210 as a metal layer by a heat treatment step (not shown). As a result, a conductive ink layer 220 containing metal particles M1 to be a conductive layer is formed on the surface of the insulating base 210.
  • a plating layer 230 is formed on the surface of the insulating base 210 through the conductive ink layer 220 by the plating step B3. More specifically, the plating layer 230 is formed by an electrolytic plating process (so-called electroplating method) using copper. Thereby, a conductive layer having the conductive ink layer 220 as the first conductive layer and the plating layer 230 as the second conductive layer is formed. That is, the printed wiring board substrate 201 shown in FIG. 14 is manufactured.
  • a resist pattern 242 is formed by performing exposure and development using a pattern mask 241 in a state where the resist 240 is laminated on the plating layer 230. Then, a portion to be a wiring pattern is covered. Thereafter, as shown in FIG. 18, an unnecessary conductive layer other than a portion to be a wiring pattern is removed by an etching step B5-1 of the wiring circuit forming step B5. Thereafter, the resist pattern 242 is stripped by a resist pattern stripping step B5-2 in the wiring circuit forming step B5.
  • the manufacturing method of the printed wiring board 203 using the printed wiring board substrate 201 of the third embodiment is not limited to the subtractive method described above. Including various other subtractive methods, semi-additive methods, and other manufacturing methods.
  • the configuration and manufacturing method of the printed wiring board 203 and the printed wiring board 203 using the printed wiring board 201 will be described in more detail.
  • insulating base material a continuous material continuous in one direction can be used. Using the continuous material, the printed wiring board substrate 201 can be manufactured in a continuous process.
  • the insulating base 210 an independent piece having a predetermined size can be used.
  • the material used as the insulating base 210 is as described above, such as polyimide, insulating rigid material, flexible material, and the like.
  • the conductive ink an ink containing fine metal particles M1 as a conductive substance and containing a dispersant for dispersing the metal particles M1 and a dispersion medium is used.
  • the type and size of the metal particles M1 dispersed in the conductive ink are as described above, except that nickel (Ni) particles of 1 to 500 nm are used.
  • the manufacturing method of the metal particle M1 includes the titanium redox method mentioned above, and the following manufacturing methods are possible.
  • the metal particles M1 can be manufactured by the above-described conventionally known methods.
  • As the reducing agent in the case of producing the metal particles M1 by the oxidation-reduction method those described above can be used.
  • the dispersant and dispersion medium contained in the conductive ink are as described above.
  • the adjustment of the particle size of the metal particles M1 and the adjustment of the conductive ink are also as described above.
  • a spin coating method As a method for applying the conductive ink in which the metal particles M1 are dispersed on the insulating substrate 210, a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method.
  • a conventionally known coating method such as a method can be used.
  • it may be applied to only a part of the insulating base 210 by screen printing, a dispenser or the like. Drying after application. Thereafter, the process proceeds to heat treatment described later.
  • the conductive ink layer 220 fixed on the base is obtained as a baked coating layer.
  • the thickness of the conductive ink layer 220 is preferably 0.05 to 2 ⁇ m.
  • the dispersant and other organic substances contained in the applied conductive ink are volatilized and decomposed by heat to be removed from the coating layer, and the remaining metal particles M1 are in a sintered state or a stage before sintering. In this state, they are firmly fixed on the insulating substrate 210 as if they were in close contact with each other and solid-bonded.
  • the heat treatment may be performed in the air.
  • the metal particles M1 in order to prevent oxidation of the metal particles M1, it may be further fired in a reducing atmosphere after firing in the air.
  • the firing temperature can be set to 700 ° C. or less from the viewpoint of suppressing the metal crystal grain size of the conductive ink layer 220 formed by the firing from being excessively increased and the generation of voids.
  • the heat treatment is performed at a temperature of 500 ° C. or less in consideration of the heat resistance of the insulating base 210.
  • the lower limit of the heat treatment temperature is preferably 150 ° C. or higher in consideration of the purpose of removing organic substances other than the metal particles M1 contained in the conductive ink from the coating layer.
  • the O 2 concentration is decreased by setting the O 2 concentration to 1000 ppm or less.
  • a non-oxidizing atmosphere can be obtained.
  • a reducing atmosphere can be obtained by containing hydrogen at a concentration lower than the lower explosion limit (3%).
  • the plating layer 230 to be laminated on the surface of the insulating base 210 via the conductive ink layer 220 is laminated by the plating step B3. Actually, it is performed by an electrolytic plating process (so-called electroplating method) using copper (Cu).
  • electrolytic plating process so-called electroplating method
  • Cu copper
  • the thickness of the plating layer 230 serves as a base formation necessary for the formation of the plating layer 230 as the second conductive layer, and as long as the front and back surfaces of the insulating base material 210 are reliably covered, the thickness may be thin. It is.
  • the plating layer 230 requires a thickness necessary for forming a printed wiring. Therefore, substantially, the thickness of the plating layer 230 can be considered as the thickness of the entire conductive layer.
  • the conductive ink layer 220 that is the first conductive layer is made of nickel (Ni).
  • the conductive ink layer 220 may be a metal having good adhesion to copper (Cu) other than nickel (Ni). However, it is desirable to use nickel (Ni).
  • the plating step B3 is configured only by the electrolytic plating step. However, an electroless plating step of covering the surface of the insulating base 210 with an electroless plating layer before the electrolytic plating step is performed. It is good also as a structure provided. With such a configuration, the thickness of the conductive ink layer 220 as the first conductive layer can be reduced. Therefore, it is possible to obtain the printed wiring board substrate 201 and the printed wiring board 203 that can save the ink amount and can reduce the cost.
  • the conductive layer is formed by the conventional sputtering method. Compared to the formed printed wiring board substrate and the printed wiring board using the printed wiring board substrate, it does not require expensive vacuum equipment for manufacturing, can reduce equipment costs, and has high production efficiency. There is no size limit. In addition, it is possible to achieve a high density, high performance, and a sufficiently thin conductive layer by using various base materials without using an organic adhesive and without being limited by the material of the base material.
  • the growth of oxide at the interface K between the insulating base 210 and the plating layer 230 can be suppressed in an oxidizing atmosphere (particularly a high-temperature oxidizing atmosphere), thereby preventing the insulating base 210 and the plating layer 230 from peeling off.
  • an oxidizing atmosphere particularly a high-temperature oxidizing atmosphere
  • the conductive ink layer 220 is formed of two types of metal particles, that is, metal particles M1 made of nickel (Ni) and metal particles M2 made of copper (Cu).
  • metal particles M1 made of nickel (Ni) the number of particles per unit area of the metal particles M1 made of nickel (Ni) dispersed and adhered to the interface K between the insulating base 210 and the plating layer 230 can be easily adjusted and more uniform. Can be dispersed and adhered.
  • the printed wiring board substrate 201 having such a configuration is placed in a high-temperature oxidizing atmosphere, as shown in the lower part of FIG. 19, only the portion where the metal particles M2 made of copper (Cu) are present at the interface K is oxidized. A copper layer X grows.
  • the copper oxide layer X can be prevented from growing in a uniform layer form at the interface K. Therefore, this non-uniform copper oxide layer X serves as an anchor effect, and a decrease in adhesion between the insulating base 210 and the plating layer 230 can be prevented. Therefore, it is possible to effectively prevent the insulating substrate 210 and the plating layer 230 from being peeled off as the oxide grows in a high-temperature oxidizing atmosphere. Therefore, a highly reliable printed wiring board substrate 201 can be obtained.
  • nickel (Ni) and copper (Cu) which are metal particles exist in the interface K with the particle shape. Therefore, when forming a printed wiring board using the printed wiring board substrate 201, etc., in the etching step B5-1, the metal particles M1 made of nickel (Ni) accompanying the etching of the metal particles M2 made of copper (Cu). Can also be etched. Therefore, much better etching properties can be realized.
  • the mixing ratio of nickel (Ni) and copper (Cu) in the conductive ink layer 20 is preferably 0.05 to 0.9 in terms of Ni / (Ni + Cu), and more preferably 0.2 to 0. .8 is desirable.
  • a conductive ink having a nickel concentration of 5% by weight in which nickel particles having a particle diameter of 40 nm are dispersed using water as a solvent is prepared and applied to the surface of a polyimide film (Kapton EN) as an insulating substrate. And dried in the air at 60 ° C. for 10 minutes. Further, heat treatment was performed at 300 ° C. for 30 minutes in a nitrogen atmosphere (oxygen concentration: 100 ppm). Further, electroless plating of copper was performed on the surface of the conductive ink layer by 0.3 ⁇ m, and further, electroplating of copper was performed, thereby obtaining a printed wiring board substrate having a thickness of 12 ⁇ m.
  • Example 5 The same heat treatment was performed as in Example 5 except that the atmosphere of heat treatment was changed to 3% hydrogen and 97% nitrogen. Further, electroless plating of copper was performed on the conductive ink layer by 0.3 ⁇ m, and further, electroplating of copper was performed to obtain a printed wiring board substrate having a thickness of 12 ⁇ m.
  • sample The following three types of samples with the same thickness and shape of the plating layer (made of copper) were used.
  • Plating layer thickness 18 ⁇ m Shape: Strip shape with a width of 1 cm
  • Sample 1 Printed wiring board substrate according to the present invention (third embodiment)
  • Sample 2 Printed wiring board substrate using only Cu by a sputtering method and not having a seed layer
  • Sample 3 Printed wiring board substrate provided with seed layer (Ni and Cr) by sputtering method
  • the printed wiring board substrate according to the third embodiment of the present invention can simultaneously realize prevention of peeling of the conductive layer in a high-temperature oxidizing atmosphere and good etching properties.
  • high-density, high-performance printed wiring board substrates and printed wiring boards can be favorably provided at low cost without the need for vacuum equipment, and industry in the field of printed wiring The above usability is high.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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PCT/JP2010/056556 2009-04-24 2010-04-13 プリント配線板用基板、プリント配線板、及びそれらの製造方法 WO2010122918A1 (ja)

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EP10766975.6A EP2424337A4 (en) 2009-04-24 2010-04-13 SUBSTRATE FOR PRINTED CARD, PRINTED CARD, AND METHODS OF MANUFACTURING THE SAME
US13/265,108 US20120031656A1 (en) 2009-04-24 2010-04-13 Substrate for printed wiring board, printed wiring board, and methods for producing same
CN201080018270.5A CN102415222B (zh) 2009-04-24 2010-04-13 用于印刷布线板的基板、印刷布线板及其制造方法
US14/185,206 US20140166495A1 (en) 2009-04-24 2014-02-20 Substrate for printed wiring board, printed wiring board, and methods for producing same
US15/213,216 US20160330847A1 (en) 2009-04-24 2016-07-18 Method for producing printed wiring board
US15/214,278 US20160330850A1 (en) 2009-04-24 2016-07-19 Method for producing printed wiring board

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JP2009106948 2009-04-24
JP2009-106948 2009-04-24
JP2009244273A JP2010272837A (ja) 2009-04-24 2009-10-23 プリント配線板用基板、プリント配線板、及びプリント配線板用基板の製造方法
JP2009-244273 2009-10-23
JP2010052570A JP5267487B2 (ja) 2010-03-10 2010-03-10 プリント配線板用基板、プリント配線板用基板の製造方法
JP2010-052570 2010-03-10
JP2010052569A JP5327107B2 (ja) 2010-03-10 2010-03-10 プリント配線板用基板、プリント配線板、プリント配線板の製造方法
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US14/185,206 Division US20140166495A1 (en) 2009-04-24 2014-02-20 Substrate for printed wiring board, printed wiring board, and methods for producing same

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